Aerobic biological degradation of organic matter and fracturing fluid additives in high salinity hydraulic fracturing wastewaters.

Reuse of hydraulic fracturing wastewaters depends on effective tailored treatment to prepare the water for the intended end use. Aerobic biological treatment of hydraulic fracturing produced water was examined to degrade dissolved organic carbon (DOC) and polyethylene glycols (PEGs). Biological treatment experiments of three produced water samples with DOC concentrations ranging from 22 to 420 mg/L and total dissolved solids (TDS) levels ranging from 26 to 157 g/L were conducted in 48-240 h batches. Samples were not pretreated to remove suspended solids and were inoculated with activated sludge and acclimated over several weeks. Results show that between 50% and 80% of DOC was removed in 12-24 h but a sizeable portion, on a mass basis, remained in the samples with higher DOC concentrations. PEGs were also shown to readily biodegrade into singly- and doubly-carboxylated metabolites, but were not shown to degrade past that point, leading to accumulation of PEG-dicarboxylates (PEG-diCs) in the batch reactors. Possible explanations include residence times that were too long, resulting in starved microbial populations (and thus, a stopping of PEG degradation) or the presence of other ethoxylated additives that degraded into PEGs and PEG-diCs and fed this accumulation. This work demonstrates that a well-acclimated microbial culture is capable of degrading a large portion of DOC in hydraulic fracturing wastewaters across a wide spectrum of TDS concentrations, indicating that biological treatment is a viable option for enabling reuse of produced water.

Investigating regime shifts and the factors controlling Total Inorganic Nitrogen concentrations in treated wastewater using non-homogeneous Hidden Markov and multinomial logistic regression models.

Total Inorganic Nitrogen (TIN) in treated wastewaters: the sum of effluent ammonia-, nitrate- and nitrite-nitrogen, is a common regulatory measure of nitrogen removal. In many parts of the United States, regulatory agencies have reduced discharge limits for TIN, recognizing the environmental and health impacts of these species. However, many permit limits are based on annual average or median values, and because temporal variability in effluent TIN is common, may not achieve water quality goals. We created a performance-based modeling approach using Hidden Markov Models and multinomial logistic regression using weekly effluent water quality data from an operating wastewater treatment facility in the US, over the period of January 1, 2010-March 31, 2014. In the two-step modeling approach, Hidden Markov Models capture temporal regime shifts in effluent TIN and multinomial logistic regression identifies prominent factors associated with the regime shifts. Simulations from the proposed Hidden Markov Model and multinomial logistic regression indicate that climate factors (temperature and precipitation), seasonality, effluent total ammonia nitrogen (TAN), and prior weeks' levels of effluent TIN are predictive of effluent TIN concentrations. The hybrid HMM-regression model correctly predicted the states of compliance (state 1) and non-compliance (state 2) with TIN limits with 84% accuracy. Further analysis using model simulations suggest that although annual average or median limits for TIN are met, this plant had a >30% probability of exceeding the annual limit on a weekly time scale, and therefore may not be reliably effective in protecting receiving water quality.

Assessment of wastewater treatment facility compliance with decreasing ammonia discharge limits using a regression tree model.

A regression tree-based diagnostic approach is developed to evaluate factors affecting US wastewater treatment plant compliance with ammonia discharge permit limits using Discharge Monthly Report (DMR) data from a sample of 106 municipal treatment plants for the period of 2004-2008. Predictor variables used to fit the regression tree are selected using random forests, and consist of the previous month's effluent ammonia, influent flow rates and plant capacity utilization. The tree models are first used to evaluate compliance with existing ammonia discharge standards at each facility and then applied assuming more stringent discharge limits, under consideration in many states. The model predicts that the ability to meet both current and future limits depends primarily on the previous month's treatment performance. With more stringent discharge limits predicted ammonia concentration relative to the discharge limit, increases. In-sample validation shows that the regression trees can provide a median classification accuracy of >70%. The regression tree model is validated using ammonia discharge data from an operating wastewater treatment plant and is able to accurately predict the observed ammonia discharge category approximately 80% of the time, indicating that the regression tree model can be applied to predict compliance for individual treatment plants providing practical guidance for utilities and regulators with an interest in controlling ammonia discharges. The proposed methodology is also used to demonstrate how to delineate reliable sources of demand and supply in a point source-to-point source nutrient credit trading scheme, as well as how planners and decision makers can set reasonable discharge limits in future.

Risk-Cost Estimation of On-Site Wastewater Treatment System Failures Using Extreme Value Analysis.

Owner resistance to increasing regulation of on-site wastewater treatment systems (OWTS), including obligatory inspections and upgrades, moratoriums and cease-and-desist orders in communities around the U.S. demonstrate the challenges associated with managing risks of inadequate performance of owner-operated wastewater treatment systems. As a result, determining appropriate and enforceable performance measures in an industry with little history of these requirements is challenging. To better support such measures, we develop a statistical method to predict lifetime failure risks, expressed as costs, in order to identify operational factors associated with costly repairs and replacement. A binomial logistic regression is used to fit data from public records of reported OWTS failures, in Boulder County, Colorado, which has 14 300 OWTS to determine the probability that an OWTS will be in a low- or high-risk category for lifetime repair and replacement costs. High-performing or low risk OWTS with repairs and replacements below the threshold of $9000 over a 40-year life are associated with more frequent inspections and upgrades following home additions. OWTS with a high risk of exceeding the repair cost threshold of $18 000 are further analyzed in a variation of extreme value analysis (EVA), Points Over Threshold (POT) where the distribution of risk-cost exceedance values are represented by a generalized Pareto distribution. The resulting threshold cost exceedance estimates for OWTS in the high-risk category over a 40-year expected life ranged from $18 000 to $44 000.

Modeling on-site wastewater treatment system performance fragility to hydroclimate stressors.

Increasing variability of climate-related factors, especially precipitation and temperature, poses special risks to on-site wastewater treatment systems (OWTS), which depend on subsurface saturation conditions for treatment and dispersion of wastewater. We assess OWTS fragility - the degree to which a system loses functionality - as a step to characterizing the resilience of residential wastewater treatment systems. We used the frequency and indexed severity of OWTS failures and resulting repairs to quantify fragility as a function of hydroclimate variables, including precipitation, temperature and stream flow. The frequency of each category of repair (minor, moderate and major) for 225 OWTS obtained from Boulder County public health records was modeled as a function of climate factors using a generalized linear model with a Poisson distribution link function. The results show that prolonged precipitation patterns, with monthly rainfall >10.16 cm, influence OWTS fragility, and complete loss of OWTS functionality, requiring replacement, is impacted by high temperatures, frequency of wetter-than-normal months, and the magnitude of peak stream flow in the watershed. Weather-related covariates explained 70% of the variability in OWTS major repair data between 1979 and 2006. These results indicate that fragility arising from climate factors, and associated costs to owners, environmental and health impacts, should be considered in planning, design and operation of OWTS.

Soluble microbial products decrease pyrite oxidation by ferric iron at pH < 2.

Research on microbial activity in acid mine drainage (AMD) has focused on transformations of iron and sulfur. However, carbon cycling, including formation of soluble microbial products (SMP) from cell growth and decay, is an important biogeochemical component of the AMD environment. Experiments were conducted to study the interaction of SMP with soluble ferric iron in acidic conditions, particularly the formation of complexes that inhibit its effectiveness as the primary oxidant of pyrite during AMD generation. The rate of pyrite oxidation by ferric iron in sterile suspensions at pH 1.8 was reduced by 87% in the presence of SMP produced from autoclaved cells at a ratio of 0.3 mg DOC per mg total soluble ferric iron. Inhibition of pyrite oxidation by SMP was shown to be comparable to, but weaker than, the effect of a chelating synthetic siderophore, DFAM. Two computational models incorporating SMP complexation were fitted to experimental results. Results suggest that bacterially produced organic matter can play a role in slowing pyrite oxidation.

Effect of average flow and capacity utilization on effluent water quality from US municipal wastewater treatment facilities.

There is increasing interest in decentralization of wastewater collection and treatment systems. However, there have been no systematic studies of the performance of small treatment facilities compared with larger plants. A statistical analysis of 4 years of discharge monthly report (DMR) data from 210 operating wastewater treatment facilities was conducted to determine the effect of average flow rate and capacity utilization on effluent biochemical oxygen demand (BOD), total suspended solids (TSS), ammonia, and fecal coliforms relative to permitted values. Relationships were quantified using generalized linear models (GLMs). Small facilities (40 m³/d) had violation rates greater than 10 times that of the largest facilities (400,000 m³/d) for BOD, TSS, and ammonia. For facilities with average flows less than 40,000 m³/d, increasing capacity utilization was correlated with increased effluent levels of BOD and TSS. Larger facilities tended to operate at flows closer to their design capacity while maintaining treatment suggesting greater efficiency.

Inhibition of perchlorate reduction by nitrate in a fixed biofilm reactor.

Perchlorate and nitrate were reduced simultaneously in fixed biofilm reactors. Reduction of 1000 microg L(-1) perchlorate decreased slightly with the addition of 10-16 mg L(-1) NO(3)-N when excess acetate was supplied while denitrification was complete. When influent acetate was reduced by 50% to well below the stoichiometric requirement, perchlorate reduction decreased by 70% while denitrification decreased by only 20%, suggesting that competition for electrons by nitrate was a factor in inhibition. Reduction of nitrate was favored over perchlorate, even though reactor biofilm had been enriched under perchlorate-reducing conditions for 10 months. When excess acetate was restored, perchlorate and nitrate returned to initial levels. The average most probable numbers of perchlorate- and nitrate-reducing bacteria during excess substrate operation were not significantly different and ranged between 2.0 x 10(5) and 7.9 x 10(5)cells cm(-2) media surface area. The effect of nitrate on chloride generation by suspensions of perchlorate-reducing populations was studied using a chloride ion probe. The rate of reduction of 2mM perchlorate decreased by 30% in the presence of 2mM nitrate when excess acetate was added. When acetate was limited, perchlorate reduction decreased by 70% in the presence of equi-molar nitrate.

Effluent recirculation to improve perchlorate reduction in a fixed biofilm reactor.

The effect of effluent recirculation on perchlorate reduction in a nominally plug-flow fixed biofilm reactor was studied in two cases: influent concentrations of 10 and 400 microg/L at low hydraulic loading rates (1.9 and 37.5 m(3)/m(2)/day without and with recirculation, respectively) and after a step increase in perchlorate concentration to 1,000 microg/L at the higher hydraulic loading rate (5 and 100 m(3)/m(2)/day without and with recirculation, respectively). Complete perchlorate reduction was sustained for influent concentrations of 400 and 10 microg/L in both flow regimes at the lower hydraulic loading rates. Reactor tracer profiles showed that biofilm diffusion had a more significant effect on mass transfer in the plug flow reactor compared with recirculation. The recirculation bioreactor acclimated more rapidly to increased hydraulic and perchlorate mass loading rates with significantly lower effluent perchlorate compared to the plug flow reactor: 16 microg/L versus 46 microg/L, respectively, although complete perchlorate removal was not achieved in either flow regime after 21 days acclimation to the higher loading. Total biofilm mass was more uniformly distributed in the recirculation reactor which may have contributed to better performance under increased perchlorate loading.

Effects of soluble ferri-hydroxide complexes on microbial neutralization of acid mine drainage.

Heterotrophic respiration of ferric iron by Acidiphilium cryptum was investigated in anoxic microcosms with initial media pH values from 1.5 to 3.5. No organic carbon consumption or iron reduction was observed with an initial pH of 1.5, indicating that A. cryptum may not be capable of iron respiration at this pH. Significant iron reduction was observed at pH 2.5 and 3.5, with different effects. When the initial pH was 3.5, pH increased to 4.7-5.5 over 60 days of incubation with simultaneous production of 0.4 g L(-1) Fe2+. However, at an initial pH of 2.5, no significant change in pH was observed during iron respiration, although the accumulation of soluble ferrous iron was significantly higher, averaging 1.1 g L(-1) Fe2+. The speciation of the ferric iron electron acceptor may explain these results. At pH values of 3.5 and higher, precipitated ferric hydroxide Fe- (OH)3 would have been the primary source of ferric iron, with reduction resulting in net production of OH- ions and the significant increases in media pH observed. However at pH 2.5, soluble complexes, FeOH2+ and Fe(OH)2+, may have been the more prevalent electron acceptors, and the alkalinity generated by reduction of complexed iron was low. The existence of charged ferri-hydroxide complexes at pH 2.5 was verified by voltammetry. Results suggest that initiation of bacterial iron reduction may result in neutralization of acid mine drainage. However, this effect is extremely sensitive to iron speciation within a relatively small and critical pH range.

Acclimation of activated sludge to degrade toxic levels of 2,4-dinitrophenol.

Biodegradation of 75 and 100 mg/l of 2,4-dinitrophenol (DNP) by activated sludge acclimated in a Sequencing Batch Reactor (SBR) consistently required less than 6 hours although a lag at the beginning of every 48-hour SBR cycle was observed. Other investigators have reported that DNP levels of 100 mg/l and higher are significantly toxic even to acclimated bacteria. The activated sludge acclimated to 75 mg/l initial DNP had over 100 times the DNP-degrading bacteria than an SBR acclimated to 10 mg/l DNP, although the MLSS concentration in both reactors was similar. Results suggest that two mechanisms are responsible for activated sludge acclimation to toxic levels of DNP: maintenance of DNP-degrading biomass sufficiently large to reduce initial DNP to non-toxic levels, allowing for subsequent rapid degradation; and extension of the aeration period well beyond the time required for degradation to prevent gradual accumulation of any by-product which might also be toxic.

Iron respiration by Acidiphilium cryptum at pH 5.

The growth of acidophilic iron respiring bacteria at pH > 4.5 may be a key to the transition from acidic to circumneutral conditions that would occur during restoration of acid mine drainage sites. Flasks containing Acidiphilium cryptum ATCC 33463 were incubated initially under aerobic conditions in liquid medium containing Fe(2)(SO(4))(3) and glucose at an initial pH of 5. Significant iron respiration was observed after flasks were sealed to prevent oxygenation; at the same time, medium pH increased from 4.5 to 6. No soluble Fe(III) was detected throughout the experiments, consistent with pH conditions, indicating that bacteria were able to respire using precipitated ferric iron species. In addition, the concentration of soluble Fe(2+) reached a plateau, even though iron respiration appeared to continue, possibly due to precipitation of mixed Fe (II)/Fe(III)-oxide as magnetite. Results suggest that A. cryptum has a wide range of pH tolerance, which may enable it to play a role in controlling acid generation by means of establishing growth conditions favorable to neutrophilic bacteria such as sulfate reduction.

Influence of heterotrophic microbial growth on biological oxidation of pyrite.

The rate and extent of pyrite oxidation by the iron-oxidizing bacteria Acidithiobacillus ferrooxidans was limited by the growth of the heterotrophic microbe Acidiphilium acidophilum. In batch systems containing a mixture of both organisms, the maximum zero-order rate of ferric iron accumulation was about 1.4 mg of Fe3+ L(-1) d(-1) as compared to 9.4 mg of Fe3+ L(-1) d(-1) for pure cultures of A. ferrooxidans under the same conditions. Pyrite oxidation was limited in cases where both cultures of organisms were initially present as well as situations where the heterotrophic organisms were added to established, pyrite-oxidizing systems containing A. ferrooxidans. Results also indicated that organic carbon remaining in solution following heterotrophic bacterial growth reduced the rate of abiotic pyrite oxidation by the ferric ion. Furthermore, a cell-free solution of the residual organic carbon resulted in a lag of A. ferrooxidans growth in soluble ferrous medium. The residual organic carbon solution that accumulated during the growth of Aph. acidophilum had a diverse molecular weight distribution, indicating that different compounds could be responsible for the inhibition of chemical pyrite oxidation and the A. ferrooxidans growth lag observed. Titration of dissolved copper ions with residual dissolved organic carbon originating from Aph. acidophilum cultures indicated that a metal complexation mechanism could be responsible for the lower rates of pyrite oxidation observed. These data suggest that encouraging the growth of heterotrophic microorganisms under acid mine drainage conditions may be a feasible strategy for decreasing both the rate and the extent of sulfide mineral oxidation.